Dimensional Metal-organic Framework Research Articles

Rational design of continuous and short-range lithium ion pathways based on polydopamine-anchored metal-organic frameworks for all-solid-state electrolytes

The immerging three dimensional (3D) metal-organic framework (MOF)-reinforced composite solid-state electrolytes have attracted great interest because of the enhanced ionic conductivity and mechanical properties. However, the defective spatial arrangement of MOFs restricted by fabrication methodology leads to insufficient lithium ion transport in electrolytes. Herein, a 3D interconnected MOF framework tailored for all-solid-state electrolytes is rationally designed by a universal polydopamine (PDA)-engineered “double-sided tape” strategy. The PDA serves as a double-sided tape, firmly adhering on the special single-layer Nylon grid as well as offering uniform nucleation sites to anchor the metal nodes to ensure continuous growth of well-ordered MOFs. Benefiting from the Lewis acid feature of MOFs and its cage effect toward TFSI−, a fast and homogeneous lithium ion transport can be achieved through the internal channels within neighboring MOFs and the continuous MOFs/polymer interfaces both along the short-range circumferential boundary of Nylon fiber. The resultant composite electrolytes exhibit high lithium ion conductivity and prominent mechanical properties, rendering excellent cyclic stability whether used in coin or pouch cells. This work demonstrates a widely applicable “double-sided tape” strategy for controllable spatial arrangement of MOF nanoparticles on optional substrates, which provides a scalable approach to rationally construct desired lithium ion pathways within composite electrolytes.

Development of conductive two-dimensional metal-organic frameworks self-cleaning membrane for enhanced antibiotics rejection and sustainable fouling mitigation

In this study, a novel electroactive NF membrane was constructed for ultrafast rejection of antibiotics with high selectivity and self-cleaning by incorporating a conductive two dimensional metal-organic frameworks (Cu-HHTP) into porous polyvinylidene fluoride (PVDF) matrix with facile and scalable non-solvent induced phase inversion strategy. Cu-HHTP membrane showed two orders of magnitude higher permeability (198.4 L m−2 h−1·bar−1) than the commercial and most reported NF membranes without sacrificing rejection toward negatively charged tetracycline (95.4 %), positively charged vancomycin (99.9 %) and neutrally charged valinomycin (99.9 %). Interestingly, loading Cu-HHTP with hydrophilic and porous nature can break the permeability-rejection trade-off effect and the mechanism was due to the improved water channel and pollutants sieving. Furthermore, it has stable antibiotics rejection and high flux recovery rate of 93.9 % for long-term filtration of wastewater over 264 h with low energy consumption of 0.1007 W h/L and without adding chemical cleaning agents, which demonstrated its excellent fouling control and stability. This study may guide the development of advanced self-cleaning NF membranes tailored for removal of small molecular emerging contaminants.

Unveiling the electronic origin of lanthanide based Metal Organic Framework with ideal spin filtering capacity

Recently, a three dimensional metal-organic framework (MOF) based on Dy(III) and the L-tartrate ligand was experimentally shown to exhibit a spin polarization (SP) power of 100% at room temperature. The material’s spin filtering ability was ascribed to the chiral-induced spin selectivity (CISS) effect. In this work, we computationally characterize the electronic structure of this MOF, revealing that the high SP of the material is linked to the asymmetric arrangement, around the Fermi level, of the alpha- and beta-spin electron states arising from the 4f-states of the lanthanide Dy atom, which results in two different conduction channels (band gaps) for each spin state. Based on the understanding gathered in this work, we propose that the substitution of the hydroxyl groups of the ligand by mercaptan groups should boost the electrical conductivity, while retaining the spin filtering power of the material.

Two dimensional Co-based metal organic framework for selective adsorption of Congo red from wastewater

Metal Organic Frameworks (MOFs) are promising candidates for adsorptive removal of dyes. Nevertheless, the synthesis of crystalline MOFs is a challenging task in achieving selective dye removal while ensuring efficient reusability. Herein, Co-MOF was synthesized by the solvothermal method and investigated using X-ray single crystallography, PXRD, IR and thermogravimetric analysis. Moreover, Co-MOF exhibits excellent removal efficiency towards Congo red. The maximum adsorption of Congo red by Co-MOF after optimizing parameters such as the effect of dye concentration, adsorbent dosages and pH was reached 974.86 mg/g. It is observed that the adsorption process follows the pseudo-second order kinetics and the adsorption isotherm fits well with the Langmuir model indicating complex adsorption process. The H-bonding, π-π interaction and electrostatic interaction play a crucial role in the adsorption mechanism. The Co-MOF has a significant recycling performance of 879.85 mg/g even after five cycles, showing potential application in wastewater treatment and developing a new class considering sustainable environment.

Correlation between Spin Effect and Catalytic Activity of Two Dimensional Metal Organic Frameworks for Oxygen Evolution Reaction

Spin state modulation has been demonstrated an effective strategy to tune the catalytic performance of metal organic frameworks for electrochemical oxygen reduction reaction (OER). However, the undisclosed correlation between spin-state...

Exploring the synthese, structure, and properties of a 3D Mn-MOF based on 4,6-bistriazole isophthalic acid

One three dimensional metal organic framework {[Mn2(BTIA)2(H2O)]·7H2O}n (Mn-1) was synthesized from the multidentate organic linker 4,6-bistriazole isophthalic acid (H2BTIA) and MnCl2·4H2O under solvothermally condition. The structure of 1 exhibits as a three-dimensional framework fabricated by the binuclear subunits [Mn2(COO)2(H2O)] and the organic linkers (H2BTIA). Topologically, it displays a binodal framework with Schläfli symbol (44·62)2(416·612), which contains one dimensional channels along a direction. The magnetic behavior of Mn-1 was investigated, which discloses the antiferromagnetic (AF) interactions between Mn2+ ions with the coupling constant J = −1.38 cm−1. In additin, the porous Mn-MOF shows a small uptake capacity for CO2.

Functionalization of chitosan biopolymer using two dimensional metal-organic frameworks and MXene for rapid, efficient, and selective removal of lead (II) and methyl blue from wastewater

The efficient elimination of lead (II) and methyl blue from aqueous media was a critical problem for humans. The removal of dyes and heavy metals, especially methylene blue and lead, from wastewater is essential for human health and the environment, and utilizing a suitable adsorbent to attain this goal is highly desirable. In the present study first time, chitosan biopolymer was functionalized using Two Dimensional Metal-Organic Frameworks (Ni3(HITP)2) and MXene for efficient, rapid, and selective removal of lead (II) and Methyl blue. To obtain an adsorbent (Ni3(HITP)2/MXene/CS), 1 g of chitosan (biopolymer) and Metal-Organic Frameworks were added in MXene dark-colored suspension and ultrasonically dispersed for 25 min. The batch sorption was carried out, and sorption behavior was analyzed. Batch sorption procedures were conducted to explore the sorption of Pb2+ and MB by Ni3(HITP)2/MXene/CS composite in 25 mL of aqueous solutions. The adsorbent utilized in the present experiments was 10 mg. The effect of the initial concentration of Pb2+ and MB was explored in the range of 10–400 mg L−1. Composite (Ni3(HITP)2/MXene/CS) had excellent sorption performance in the range of pH= 3–6 for lead (II) and pH= 2–9 for methyl blue. The maximum adsorption capacity for lead (II) was 448.93 mg g− 1 at 298 K, 400.59 mg g− 1 at 308 K, and 305.80 mg g− 1 at 318 K. In contrast, the maximum sorption capability for methyl blue was 424.99 mg g− 1 at 298 K, 354.03 mg g− 1 at 308 K, and 251.78 mg g− 1 at 318 K. The sorption of lead (II) and methyl blue on Ni3(HITP)2/MXene/CS composite conformed to pseudo-second-order kinetic and Langmuir model. These outcomes verified that Ni3(HITP)2/MXene/CS composite was selectivity efficient, and quick removal of Methylene blue and lead from wastewater, which is of practical importance.

Proposal of spin crossover as a reversible switch of catalytic activity for the oxygen evolution reaction in two dimensional metal-organic frameworks.

The development of oxygen evolution reaction (OER) catalysts with high activity and controllability is crucial for clean energy conversion and storage but remains a challenge. Here, based on first-principles calculations, we propose to utilize spin crossover (SCO) in two-dimensional (2D) metal-organic frameworks (MOFs) to achieve reversible control of OER catalytic activity. The theoretical design of a 2D square lattice MOF with Co as nodes and tetrakis-substituted cyanimino squaric acid (TCSA) as ligands, which transforms between the high spin (HS) and the low spin (LS) state by applying an external strain (∼2%), confirms our proposal. In particular, the HS-LS spin state transition of Co(TCSA) considerably regulates the adsorption strength of the key intermediate HO* in the OER process, resulting in a significant reduction of the overpotential from 0.62 V in the HS state to 0.32 V in the LS state, thus realizing a reversible switch for the activity of the OER. Moreover, the high activity of the LS state is confirmed by microkinetic and constant potential method simulations.

Fine-Tuning the Electrocatalytic Regeneration of NADH Cofactor Using [Rh(Cp*)(bpy)Cl]+-Functionalized Metal-Organic Framework Films.

Electrochemical regeneration of the reduced form of the nicotinamide adenine dinucleotide (NADH) cofactor catalyzed by immobilized [Rh(Cp*)(bpy)Cl]+ is a promising approach for the enzymatic synthesis of many valuable chemicals with NAD-dependent dehydrogenases. However, rational control of the efficiency is often limited by the irregular structure of the electrode/electrolyte interface and the accessibility of the molecular catalyst. Here, we propose an electrochemical system for NADH cofactor regeneration, based on highly ordered three- dimensional (3D) metal-organic framework (NU-1000) films. [Rh(Cp*)(bpy)Cl]+ is incorporated at the zirconium nodes of NU-1000 via solvent-assisted ligand incorporation (SALI), leading to a diffusion-controlled behavior, associated with an electron hopping mechanism. Varying the ratio of redox-active [Rh(Cp*)(bpy)Cl]+ and inactive postgrafting agents enables the elaboration of functional electrodes with tunable electrocatalytic activity for NADH regeneration. The exceptionally high faradic efficiency of 97%, associated with a very high turnover frequency (TOF) of ∼1400 h-1 for NADH regeneration, and the total turnover number (TTN) of over 20000 for the enzymatic conversion from pyruvate to l-lactate, when coupled with l-lactate dehydrogenases (LDH) as a model reaction, open up promising perspectives for employing these electrodes in various alternative bioelectrosynthesis approaches.

2D metal–organic frameworks and their derivatives for the oxygen evolution reaction

Electrocatalytic oxygen evolution reaction (OER) is a critical half reaction for energy conversion and storage technologies such as water electrolysis, rechargeable metal–air batteries, carbon dioxide reduction reaction, and so on. Unfortunately, large overpotential is needed to overcome the sluggish kinetics of OER. With ultra-thin thickness, large specific surface area, rich and adjustable pore structure, and well-defined metal centers, two dimensional (2D) metal-organic frameworks (MOFs) have been widely investigated for OER. By virtue of the desirable chemical composition and diverse structural type, 2D MOFs are also employed as precursors and sacrificial templates to prepare metal-decorated porous carbon, metal oxides, metal hydroxides, metal sulfides, metal phosphides, and so on. These 2D MOFs derivatives with high surface area and abundant metal sites exhibit excellent OER performance. Herein, the current advances on 2D MOFs and their derivatives as (pre)electrocatalysts are summarized, including the synthetic strategy and OER performance. Moreover, the structure-performance relationships and actual active species or sites of 2D MOFs and their derivatives toward OER are discussed. The current scientific and technological challenges and future perspectives related with 2D MOF and their derivatives in practical applications are also mentioned at last.

One dimensional terpyridine-based metal organic framework for stable supercapacitor

In summary, a novel structure of MOF based on 1,4–di ([2,2':6',2''terpyridin] -4'-yl)benzene and 1,4-naphthalenedicarboxylic acid has been constructed through hydrothermal reaction. The Ni-MOF displays one dimensional zigzag chain, which connect each other by hydrogen bonding to form three dimensional supramolecule with large channels. The conjugated systems of the terpyridin and benzene ligands enhance the chain rigidity, accelerate the electron transport. The massive channels provides electrolyte rapid transfer. By the structural feature aforementioned, the Ni-MOF demonstrates stable electrochemical performance as suprocapacitor.

Two–dimensional metal organic nanosheet as promising electrocatalysts for carbon dioxide reduction: A computational study

Designing high–selectivity and low-cost electrocatalysts are highly desirable for the carbon dioxide reduction reaction (CO2RR). Herein, the promising CO2RR electrocatalysts were screened out from several two–dimensional metal organic frameworks (2D–MOFs) nanosheets by means of density functional theory (DFT) calculations. According to the computational results, we identified three promising CO2RR catalysts for different products. The main products of CO2RR by Fe3(HHTP)2, Co3(HHTP)2 and Ir3(HHTP)2 are HCOOH, CH3OH and CH4, respectively. Particularly, the Ir3(HHTP)2 shows remarkable high catalytic activity with lowest limiting potential (UL = –0.22 V) for CH4 production. Therefore, the rational controlled chemical modifications of 2D–MOFs materials provide a new scenario for the design of promising novel CO2RR electrocatalyst.

Theoretical Insights on the Two-Dimensional Transitional Metal Trihydroxytriaminophenalenyl for Highly Efficient Carbon Dioxide Electroreduction

Nowadays, to relieve the environmental issues and the energy depletion, one of the most practicable and feasible technologies is the electrochemical reduction of CO2 to high value added chemicals. In this aspect, the bottleneck is to develop novel catalysts with high efficiency and selectivity. Based on this idea, in this work, a series of two dimensional transitional metal doped trihydroxytriaminophenalenyl, i.e., M3(THTAP)2, have been studied as the catalysts for CO2 reduction reaction (CO2RR). Our study showed that these catalysts are stable and have metallic character, which is conducive to electroreduction reaction. Products CH4, CH3OH and HCOOH are obtained for the studied catalysts. Cr3(THTAP)2 is the best catalyst for producing CH4. Ir3(THTAP)2 produces CH3OH as the final product and the overpotential is 0.34 V. Both Pt3(THTAP)2 and Pd3(THTAP)2 are good CO2RR catalysts to produce HCOOH with the small overpotentials of 0.17 and 0.23 V, respectively. Thus, these two dimensional transition metal organic frameworks exhibit great potential as the electrochemical catalysts for high performance CO2 electro-catalytic process. We anticipate that this work may shed new light on the development of high performance metal organic framework based electrocatalysts.

Synthesis of various dimensional metal organic frameworks (MOFs) and their hybrid composites for emerging applications – A review

Metal organic frameworks (MOFs) represent the organic and inorganic hybrid porous materials. MOFs are low dense and highly porous materials which in turn provide large surface area that can accumulate and store numerous molecules within the pores. The pore size may also act as a mesh to separate molecules. The porous nature of MOFs is beneficial for altering the intrinsic properties of the materials. Over the past decade, different types of hybrid MOFs have been reported in combination with polymers, carbon materials, metal nanoparticles, metal oxides, and biomolecules for various applications. MOFs have also been used in the fabrication of electronic devices, sensors, energy storage, gas separation, supercapacitors, drug delivery and environmental clean-up. In this review, the unique structural orientation, exceptional properties and recent applications of MOFs have been discussed in the first section along with their porosity, stability and other influencing factors. In addition, various methods and techniques involved in the synthesis and designing of MOFs such as solvothermal, electrochemical, mechanochemical, ultrasonication and microwave methods are highlighted. In order to understand the scientific feasibility of MOFs in developing new products, various strategies have been applied to obtain different dimensional MOFs (0D, 1D, 2D and 3D) and their composite materials are also been conferred. Finally, the future prospects of MOFs, remaining challenges, research gaps and possible solutions that need to be addressed by advanced experimental design, computational models, simulation techniques and theoretical concepts have been deliberated.

A facile synthesis of 2D iron bridged trimesic acid based MOFs for superior nitrate and phosphate retention

The surplus concentration levels of phosphate (PO43-) and nitrate (NO3-) in potable water sources lead to eutrophication and methemoglobinemia. Currently, the selective adsorbents were applied on the basis of enriched porous nature along with the highly open metal sites. Hence, the present study was planned to develop iron(III) linked trimesic acid (FTA) as two dimensional (2D) metal organic frameworks (MOFs) (FTA MOFs) for the rapid removal of soluble fertilizers. The developed 2D FTA MOFs possesses the enhanced adsorption capacities of 55.021 ± 0.03 and 72.342 ± 0.01 mg/g towards NO3- and PO43- respectively. Thermal property, crystallinity, functional groups, porous surface nature and elemental formation of FTA MOFs was explored using TGA, XRD, DTA, FTIR, BET and EDAX. The formation of surface complex and electrostatic attraction was governed during adsorption process. The nature of nitrate and phosphate adsorption is spontaneous and endothermic. The FTA MOFs showed the good results by studying with the collected water which ensures field suitability. The proposed FTA MOFs acts as beneficial and reusable tool for fertilizers adsorption in field environment.

Ultra-stable two-dimensional metal-organic frameworks for photocatalytic H2 production.

Two-dimensional (2D) metal-organic frameworks (MOFs) are some of the most promising photocatalysts owing to their high numbers of exposed active sites and excellent charge mobility. However, the synthesis of highly stable 2D MOF photocatalysts involves challenges, and examples have been rarely reported. Herein, a new kind of material, 2D indium-based porphyrin MOF cubic nanosheets (2D In-TCPP NS) with an average thickness of ∼3.97 nm, is synthesized via a surfactant-assisted approach, and it shows good chemical stability in the pH range of 2-11 in aqueous solution. In photocatalytic H2-generation experiments, 2D In-TCPP NS exhibits activity that is enhanced by over one order of magnitude compared with the 3D bulk In-TCPP MOF, arising from its highly enhanced electron-hole separation abilities. Moreover, after 40 h of continuous photocatalysis testing, 2D In-TCPP NS shows nearly no activity decrease, which suggests its great potential for practical commercial use.

An ultrathin 2D Yb(III) metal-organic frameworks with strong electrochemiluminescence as a “on-off-on” platform for detection of picric acid and berberine chloride form

To investigate the strong electrochemiluminescence (ECL) of ultrathin two dimensional metal-organic frameworks (2D MOFs) is crucial. In this work, we reported the strong ECL behavior of 2D Yb-MOFs, which exhibited thickness-dependent ECL. The thinner the 2D Yb-MOFs, the stronger the ECL signals. The corresponding ECL emission mechanism was investigated in detail, which was ascribed to the thinner 2D Yb-MOF with larger specific surface area, provided more luminophores, better electronic conductivity and superior fluorescence quantum yield, which yielded a higher ECL intensity. Considering the excellent ECL performances above, the ultrathin 2D Yb-MOF-1 was selected as new ECL emitter so that a sensor could be fabricated to realize the “on-off-on” detection of picric acid (PA) and berberine chloride form (BCF). The proposed sensor strategy exhibited a good analytical performance, where the linear range for PA detection was from 0.1 μM to 1 μM with a limit of 81.3 nM, and that for BCF detection from 0.05 μM to 1 μM with a limit of 36.5 nM. This study carves out a novel avenue for exploiting excellent ECL materials.

Bimetallic oxygen electrocatalyst derived from metallocenes doped MOFs

Herein, metallocens (ferrocene, ruthenocene and cobaltocene) were in situ hybridized with two dimensional metal-organic frameworks (MOFs) via an improved inter-diffusion approach. The metallocens@MOFs hybrids were direct carbonized and transformed to Fe(Ru,Co)–Co@C composites. These bimetallic electrocatalysts show remarkable oxygen evolution reaction (OER) activity by taking advantage of the synergetic effect between the binary metals. Among of them, the obtained Fe–Co@C exhibits lower overpotential (320 mV at 10 mA cm−2) and satisfactory stability toward OER. The study presents a novel and facile strategy to synthesize low-cost bimetallic catalyst, showing great promise in electrocatalysis of oxygen.

Highly Stable Trimetallic (Co, Ni, and Fe) Zeolite Imidazolate Framework Microfibers: An Excellent Electrocatalyst for Water Oxidation

One dimensional (1D) metal organic framework (MOF) micro/nanostructural arrays are highly promising candidates for their potential applications in energy related areas. These exceptional behaviors ...

Throwing light on the current developments of two-dimensional metal–organic framework nanosheets (2D MONs)

Current advancements in the chemistry of two dimensional metal organic framework nanosheets (2D MONs) are sketched out in this perspective.